Alkyl-aryl diisocyanates with reduced activity



United States Patent O ALKYL-ARYL DIISOCYANATES WITH REDUCED ACTIVITY Otto Stallmann, Bridgeton, N. L, assignor to E. I. du

Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware v No Drawing. Application July 21, 1952., Serial No. 300,128

- 2 Claims Cl. 260-453 desirable reactions by carefully controlling the various steps such as order off addition, temperature, presence of moisture and the like in order to avoid undesirable side reactions.

Heretofore many attempts have been made to reduce the activity of the diisocyanates by various means including blocking or hindering one of the NCO groups. One such suggested method involves reacting the isocyanate group with a phenol or a compound containingmethylene hydrogen such as a malonic ester to form adducts which regenerate the NCO group on heating to about ISO-180 C. Among the compounds which maybe used to form mono adducts of diisocyanates are aceto-acetic ester; diethyl malonate; mercaptans such as Z-mercapto benzothiazole; lactams; imides such as succinimide,

phthalimide and the like; tertiary amyl alcohol; dimethyl phenyl carbinol; and secondary amines such as diphenylamine. These adducts regenerate -NCO groups on heating to ll50 C. j

It is also Well known that dimeric aromatic isocyanates such as the dimer of phenyl isocyanate regenerate the original isocyanate on heating to 150-180 C.

Both the adduct and dimer methods of forming blocked isocyanate groups require heating to a high temperature to free the isocyanate group. Unfortunately, this, ,is

frequently impossible due to various reasonssuch as the shape-and dimensions of the object containing them whichpreclude placing the object in anoven, or due to the adverse effects on the objects by high temperatures. These requirements for the liberation of the --NCO group obviously place restrictions and inconvenience on their use.

It is therefore an object of the present invention to reduce the activity of oneof the --NCO groups in organic diisocyanates at temperatures below about 85- C. Another object is the provision of a diisocyanate having one relatively active NCO and one relatively inactive --NCO group. Other objects will be apparent as the description of the invention proceeds.

These and other objects are accomplished by compounds which have the general formula:

. R1 r oou -arx d-nooi ,7 in which Ar is an aromatic nucleus which maybe sub? stituted or unsubstituted;' R1 and R2 are aliphatic hy- 2,729,666 Patented Jan. 3, 1956 lCC drocarbons having up to 8 carbon atoms which together with the carbon atom may form part of a cycloaliphatic ring such as cyclohexyl; and X is a bridging means which may be a simple chemical bond or an alkylene, arylene, polyvalent non-metallic element, hetero group i. e. a group containing a hetero atom, etc.

The aromatic nucleus is preferably the benzene ring although the naphthalene ring is quite usable as well as the anthracene and more complex ring systems. .The aromatic ring may be substituted with groups which are non-reactive with -NCO groups such as alkyl or halogen. Thealkyl groupsattached to the tertiary aliphatic carbon bearing the -NCO group are usually selected from methyl, ethyl, propyl, isopropyl, butyl, etc. Since the principal function is to shield the NCO group, there is no object in having too long a chain length in these groups. About 68 carbon atoms may be considered a practical upper limit above which preparation is more difiicult and no advantage is obtained. On the other hand, the two bonds together with the carbon atom may form part of a cyclo aliphatic radical such as a cyclohexyl group. I

The bridging means X is not per se a critical part of the compound. The character of the bridge does affect other characteristics "such as. solubility in various solvents and whether the diisocyanate is a liquid or a solid. The following types are representative, but other divalent groups may be used:

' TABLE 1' Simple CC bond 7 -(CHa)n-, where n is an integer from 1 to 8 Several general methods are useful for the preparation of starting materials from which the diisocyanates of this invention can 'be made. One method, disclosed by H. B. Hass and co-workers (J. Am. Chem. Soc. 71, 2290 and 3482), is based on the carbon alkylation which occurs when p- (or 0-) nitrobenzylchloride, or the corresponding nitrohalogen compounds in which the halogen is separated from the aromatic nucleus by a higher alkyl bridge, are reacted under controlled conditions with the alkali metal salts of secondary nitroparaiiins. The dinitro compounds thus obtained can readily be reduced to the diamines from which typical diisocyanates of this invention can be made by phosgenation.

Another method takes advantage of the Hofmanns degradation method for making amines from acid amides, with the refinements reported in 1930 by Montague and Casteran (Compt. rend. 191, 139) and by C. Mentzer (Compt. rend. 213, 581) who applied this method successfully to the preparation of aryl-tert. alkylamines from the corresponding acid amides. Diamines which by phosgenation give the diisocyanates of this invention, can be prepared by nitrating the above-mentioned monoamines (after the amino group has been protected, for instance by acetylation), whereby a nitro "grou is introduced in the aromatic part of the molecule, followed by reduction of the nitro to the amino group, and removing the protecting" group from the aliphatic amine by hydrolysis. In some cases, the. nitroaryl-tert. alkylamines can be. directly synthesized by subjecting the corresponding acid amides containing a nitro group asa substituent in the aromatic partof the mcleculeto the Hofmann degradation process, followed by: reduction. of the resultingnitro-amino compounds to. the desired diamines;

A useful method by: which pertinentdia'mines can be synthesized,- takes: advantage ofthe reaction disclosed in 1948 by Ritter and Kalish-inlJ; Am. Chem. Soc. 70, 4048. According to this method; tertiary mono-carbinamines are obtained. by hydrolysis of the. corresponding N-alkyl forrnamides which, in turn; arematde by reacting-tertiary alcohols inatmixtur'e ofi acetiea'cidtand sulfuric acid-with sodium cyanide. The desired amines can be obtained either by using from the star-t a nitro aryl tertiary akyl' aleohol. which is' subjected to the kitten reaction, followed byv reduction of the nitro-amino compound; or else' the nitro group can later. be introduced into' the aryl nucleus by the above-indicated method-involving nitration of the carbinamine, followed byv reduction and hydrolysis.

The phosgenation' off the diamines iscarried out in the usual manner,- for instance; by treating the dihydrochloridesof the diamines', suspended ordi'ssol'ved 'in common solventssuch-as toluene or. o-dichlorobenzene, at elevated temperatures with phosgene gas.

Typical examples of'thesc dii'socya'nates; are:

OCN-Q-(JIIaCHa-i-NCO which may be made by reducing 3-methyl-3-nitro-1-(pnitro-phenyl)-butane (J. Am. Chem. Soc. 71, page 3485) to the diamine which can be converted to the dihydrochloride and phosgenated by the method disclosed in Exwhichis made by phosgeuatingthc corresponding diamine. This diamine may be prepared by nitrating the acetylated mono-amine which is made: from the below-described tertiary alcohol by the above-described Ritter reaction, followed by reduction and'hydrolysis. The. tertiary alcohol' is made by subjecting biphenyl p-carboxylic acid methyl ester to a- Grignard reaction with: magnesium methyliodide, similar to the method disclosed by Schlenk (Ann. 368'; 298 299) for synth'es'iziri'g'- the corresponding triarylcarb'inol compound The nitro group also can first be introduced in the aromatic part of; the molecule by nitrating the tertiary alcohol, replacing the aliphatic hydroxy group. with the amino group by the Ritter reaction, and then. reducing, the nitro-amino compound to the desired. diamine 4) car-- sen, 1- e wearers Q which may be prepared by reacting 4-nitrobenzoic acid chloride. withv the. sodium, saltof. Z-nitropropane, reducing the dinitro compound to the corresponding diamine and phosgenating.

which. may be. prepared by reacting 2-nitrobutane with iodine, and potassium iodide to give 2-nitro-2-iodo-butane which is then reactedv with the sodium salt of p-aminophenol, the nitro group is reduced to the amine andthe resulting diamine is phosgenated.

which may be preparedby treating alphavnitronaphthalene with formaldehyde and hydrochloric. acid to form. L nitro-S-chloromethyl naphthalene which is then reacted with the sodium salt of 2anitropropane. Thedinitro compound. is. hydrogenated. to. the diamine and then phosgenated. Otherv types are illustrated in the examples.

The. organic diisocyanates. of this. invention have the very importantlcharacteristic of havingone -NCO group whichreacts, normally with compounds containing active hydrogen. atoms, i. e., OH,.-NHz,,-COOH-, NH-, etc.,. and having one.-NCOv group which, is. shielded. and lessreactive at ordinary temperatures-,that is, in the range of 1540 C. The shielded-NCO group, however, will react when the temperature is raised to: about -90 C.

In the case of strongly basic. lower aliphatic amines, specifically those with less than-4 carbon atoms, the shielded NCO group will react at temperatures lower than 70-90.? Cr. These compoundsare; an. exception to the generalilack ofl'reactivity'shownby compounds containing active hydrogentowardstheshielded -NCO: group at temperatures below 70-=90 C.

These diis'ocyanates' are thus very' valuable reactants in a number of instances where it is desirable to react preferentially one end of a bifunctional molecule with one compound and then react. the other end'with a different compound. Isocyanate groups are particularly valuable in many applications because theyreact with a. number oflgroups by the formation of urethane. or meat type 1inkages without the. formation. of. byproducts. In this particular' respectthe diisocyanates: are considerably superior to. the adductsof the; prior art: where. onemolecule of a foreign material is generated forv each NCO' group freed.

Furthermore, the shieldedNCO group of these new diisocyanates, while inert at roomtemperature, becomes available for reaction normally at temperatures as low as 70-75 C., compared-.to 10.0-15.0, C. required for the adducts. This is obviously a tremendous advantage. These alkyl shielded -NCO groups also appear to have a. sharper line of demarcation between their active and erases-s inactive temperature ranges than do the shielded aromatic --NCO groups of the prior art.

The outstanding superiority of the diisocyanates of this invention over the known aromatic diisocyanates in which one of the -NCO groups is shielded by a methyl group in ortho position, was strikingly demonstrated in a practical test when an attempt was made to employ the best available aromatic diisocyanate with a shielded NCO group (toluene-2,4-diisocyanate) as the cross-linking and heat-hardening agent in a lacquer based on castor oil modified alkyd resin. Almost immediately after the addition of the aromatic diisocyanate, and before this lacquer could be applied to the metal surface, both isocyanate groups in the toluenediisocyanate reacted at room temperature with the free hydroxy group in the film-forming resin, causing premature cross-linking and complete gelling of the lacquer. However, when the product of Example I was used as the cross-linking agent under otherwise strictly comparable conditions, the lacquer remained in very satisfactory condition and was without any difficulty applied (after 16 hours of storage at room temperature) to the metal surface by the conventional spraying technique. A simple heat curing treatment produced on the coated metal surface a uniformly hardened enamel of outstandingly good properties.

The following examples are given by way of illustration, but it is to be understood the invention is not limited to these specific examples, since any of the bridging groups mentioned above may be introduced as indicated by correspondingly varying the procedures given in the examples. It will also be understood that where the tertiary carbon has two methyl groups attached to it in Example I, these may be replaced by other aliphatic hydrocarbon groups having up to 8 carbon atoms.

Example I 50 parts of p-(Z-aminoisobutyl) aniline, prepared 'according to J. A. C. S. 71, 2291 (1949), was dissolved in 1430 parts of o-dichlorobenzene and was gassed with HCl at room temperature until no more amine-dihydrochloride was formed, which required about 2 hours. The suspension of crystalline dihydrochloride was heated to 130 C. and 341 parts of phosgene was passed in while stirring during the course of 6 hours at 130135 C. A clear pale yellow solution resulted. Dried nitrogen was passed through to remove dissolved phosgene and the o-dichlorobenzene was distilled off under 8 mm. pressure. The crude residue was a pale brown oil weighing 72 parts. This was fractionated at 8 mm. pressure and 57 parts boiling at 145-146 C. was collected as the main fraction. It was a water white liquid of pleasant odor analyzed 39.2% -NCO compared to a calculated value of 38.85% for a compound of the formula:

The analysis was made in the conventional manner by titration with n'butylamine.

When the diamine in which one of the methyl groups is replaced by an ethyl group (disclosed in J. Am. Chem. Soc. 71, page 2291) is phosgenated by the same procedure, the corresponding diisocyanate is obtained.

Example I! 50 parts of alpha-(l-aminocyclohexyl)-p-toluidine, prepared according to J. A. C. S. 71, 2291 (1949), was dissolved in 1300 parts of o-dichlorobenzene and gaseous I-ICl was passed in at room temperature until no more amine-dihydrochloride precipitated. The crystalline suspension was heated to 100 C. and 230 parts of phosgene was passed in while stirring and gradually raising the temperature from 100 to 130 C. over a period of 4 hours. A clear pale yellow solution was obtained. Dry

nitrogen was blown through the solution vto remove dis} solved phosgene and the o-dichlorobenze'ne was distilled off at 24 mm. pressure and a final temperature of 100 C. 61 parts of a pale brown oil was obtained. This was fractionated at 3 mm, and 58 parts of a main fraction boiling at 168-169 C. was collected. It was a water white liquid of pleasant odor which was soluble in dioxane, benzene, and ether. Analysis for --NCO showed 33.0% compared to a calculated value of 32.8% for pentyl radical instead of cyclohexyl, is obtained by phos- V genating the corresponding diamine which is also disclosed in J. Am. Chem. Soc. 71, page 2291.

The hindered diisocyanates prepared according to the present invention are useful when it is desired to carry out a reaction partially and to reserve one --NCO group for subsequent reaction. In this manner lacquers and adhesives may be formulated at room temperature in which the aromatic -NCO group is reacted with an active hydrogen of one of the components. The product may then be applied to a surface as a lacquer or as an adhesive. After the solvent has been allowed to evaporate, if one is used, the surface is then heated to 70-90 C., whereupon the alkyl --NCO group reacts with other active hydrogen groups to cross-link and form insoluble resms.

In the past, lacquers or adhesives made up with unhindered diisocyanates had a very short useful pot life which seldom was over l-4 hours without setting up. When the hindered diisocyanates of the present invention are employed, the products remain useable for 24 hours, and under some conditions, this time may be extended to 48 to 60 hours. Another advantage of the present invention is that the hindered alkyl --NCO group is affected very slowly by water, and hence it is unnecessary to exclude moist air.

The diisocyanates of the present invention are also useful as anchoring substance. The aromatic --NCO group may be reacted with a component such as a waterrepellant or a dye, and this reacted product may be applied to a substrate containing active hydrogen atoms, such as cellulosic material, and then heated to 90 C. to activate the hindered alkyl -NCO group which ultimately gives a chemical bond between the coating and the substrate.

The products of the present invention may also be used in a similar manner for manufacturing molded articles which can be cured by heating to 70-90 C.

It will be apparent that many widely difierent embodiments of this invention may be made without departing from the spirit and scope thereof, and therefore it is not intended to be limited except as indicated in the appended claims.

I claim:

1. An organic diisocyanate having one of its -NCO groups attached to an aromatic radical and its other --NCO group attached to a carbon bearing two lower aliphatic hydrocarbon groups which may be joined together to form a cycloaliphatic ring with the attached carbon, the said carbon being attached to the said aromatic radical.

2. A diisocyanate having the following formula:

in which Ar is an aromatic nucleus; the Rs are aliphatic may be. joined togethen tb form a. cycloaliphatic rigg References Citeiin the. file ofithispaient with. the attached: carbqn; and X'is. sel'ected fiom. the U IT v (A up gro'up consistiiagl ofa bond, an alkyknemadical', i 'ITES ATENTS' an ar-yle'n'e radical, a p'oIyvaIent' non-metallic el'eme'nt', hchmldtetand a biyal'gnt radibal' having a g'o'lyylnf nqmmetalli 5 OTHER REFERENCES element mtermptmg a carbon cham' Bayer: Angew. Chem, vol; 59. (September 1947), pg; 

1. AN ORGANIC DIISOCYANATE HAVING ONE OF ITS-NCO GROUPS ATTACHED TO AN AROMATIC RADICAL AND ITS OTHER -NCO GROUP ATTACTED TO A CARBON BEARING TWO LOWER ALIPHATIC HYDROCARBON GROUPS WHICH MAY BE JOINED TOGETHER TO FROM A CYCLOALIPHATIC RING WITH THE ATTACHED CARBON, THE SAID CARBON BEING ATTACTED TO THE SAID AROMATIC RADICAL. 